Recently we have investigated the formation of novel thick, solid, mesostructured films of polymer/surfactant mixtures which form spontaneously at the air-solution interface. Here we report studies of the effect of adding a series of sparingly soluble species to the precursor solution, to alter the mesostructure of cetyltrimethylammonium bromide/polyethylenimine films and to investigate the incorporation of small molecules within the films. Small-angle neutron scattering confirmed that cyclohexane and decane evenly swell the micelles in film forming solutions, while cyclohexanol extends the prolate micelles along their long axis. Although the presence of these additives in solution did not greatly affect the formation of the film, it was observed that they did influence the structure of the films. Films produced with decane consisted of a cubic phase rather the conventional 2-D hexagonal phase, whilst both cyclohexane and cyclohexanol enhance the level of ordering in low MW polymer films. Benzene was found to have no significant effect on the film. (C) 2007 Elsevier Inc. All rights reserved.